Di(carboxylic acid ester)-phenyl-azo-naphthol dyes

ABSTRACT

Acid dyes derived from aminobenzene dicarboxylic acid esters and 1-hydroxy-7-amino-naphthalene-3-sulfonic acid, particularly for dyeing wool or textile material of synthetic linear polyamides.

United States Patent l 72 l Inventors Johannes Dehnert;

Gerhard Gnad, both of Ludwigshafen, Germany [2]] Appl. No. 779,652

[22] Filed Nov. 27, 1968 [45] Patented Nov. 30, 1971 [73] Assignee Badlsche Anilin & Soda-Fabrik Aktiengesellschaft Ludwigshafen/Rhine, Germany [32] Priority Dec. 1, 1967 l 3 3 I Germany [54] DI(CARBOXYLIC ACID ESTER)-PHENYL-AZO- [51 1 Int. Cl C07c 107/08,

[ 50] Field of Search 260/ l 99 [56] References Cited UNITED STATES PATENTS 3,413,280 l0/l968 Montn'iollin et al. 260/199 X FOREIGN PATENTS 402,229 3/1966 Switzerland 260/193 Primary Examiner-Charles B. Parker Assistant E.raminerWarren C. F. Attorney-Mama", Johnston, Cook & Root ABSTRACT: Acid dyes derived from aminobenzenc dicarboxylic acid esters and l-hydroxy-7-amino-naphthalenc-Ii-sulfonic acid, particularly for dyeing wool or textile material of synthetic linear polyamides.

DI(CARBOXYLIC AClDESTEm-PHENYL-AZO- NAPHTHOL DYES This invention relates to new monoazo dyes having the general formula (I):

ROOC

lIO-

where the radicals R may be identical or different and each denotes an unsubstituted or. substituted alkyl, aralkyl or cycloalkyl radical and X denotes hydrogen, sodium orpotassium.

Examples of the radicals R are methyl, ethyl, n-propyl, isopropyl, n-butyl. isobutyl, tert-butyl, benzyl, phenylethyl and cyclohexyl.

The radicals R may bear as substituents for example hydroxy, alkoxy or aroxy groups or halogen. Examples of specific substituents are chlorine, methoxy, ethoxy, 2-methoxyethoxy, butoxy and phenoxy.

Examples of substituted radicals R are chloroethyl, methoxyethyl, ethoxyethyl, butoxyethyl, phenoxyethyl, methoxyethoxyethyl and ethoxy-ethoxyethyl.

Dyes which have special industrial importance have the general formula (Ia):

R OOC R OOC where each R denotes an alkyl radical having one to four carbon atoms, a methoxyethyl, ethoxyethyl, butoxyethyl. methoxyethoxyethyl (CH,CH OCH CH -OCH,) or ethoxyethoxyethyl (CH CH,OCH CH,-OCH,CH,) group and X denotes hydrogen, sodium or potassium.

The new dyes are eminently suitable for dyeing fibers and textile material of synthetic polyamides such as nylon 6 or nylon 6,6 and wool. Dyeings obtained therewith have excellent fastnesses, particularly light fastness, wet fastness and thermal resistance.

The new dyes can be obtained by the reaction of diazo compounds of amines having the general formula (ll):

ROOC

ROOC

diethyl 3-aminophthalate, di-n-propyl 3- yl S-aminoisophthalate, diisobutyl aminoterephthalate, di-(B- .ethoxyethyl) I aminoterephthalate, di-(fi-phenoxyethyl) aminoterephthalate, dibenzyl aminoterephthalate, dicyclohexyl aminoterephthalate, dibenzyl aminoterephthalate. dicyclohexyl aminoterephthalate and diisopropyl 5- aminoisophthlate.

The compounds having the formula (II) may be diazotised in the usual way, for example in the presence of dilute hydrochloric or sulfuric acid in water with or without dispersing agents, in organic solvents such as glacial acetic acid or in mixtures of water and organic solvents.

A pH value as faras possible in the acid range is chosen for coupling.

The invention is illustrated by the following examples. Parts and percentages in the examples are by weight unless otherwise specified.

EXAMPLE 1 .200 parts of ice is added to a solution of 20.9 parts of dimethyl S-aminoisophthalate in 300 parts of water and 25 parts by volume of concentrated hydrochloric acid and then 30 parts of 23 percent sodium nitrite solution is allowed to flow in slowly at 0 to 5 C. The whole is stirred for another two hours at the same temperature and any excess of nitrous acid is removed as usual. A solution of the sodium salt of 24.3 parts of 7-amino-l-hydroxynaphthalene-3-sulfonic acid in 300 parts by volume of water is slowly added to the diazo solution. A pH value of 4 is then set up by adding concentrated aqueous sodium acetate solution. After coupling is over, the precipitated dyes having the formula COOCIln l COOCH: H0-

SOsNB is suction filtered, washed with l0 percent sodium chloride solution and dried. A red powder is obtained which dissolves in water with a red color and dyes polyamide cloth red shades having very good fastness properties.

With the same coupling component and the diazo components given in the following table I, dyes which give very fast dyeings on polyamides are obtained analogously.

EXAMPLE 7 26.6 parts of di-n-propyl aminoterephthalate is stirred intensely with 300 parts of water and 0.5 part of the reaction product of oleylamine with about 12 moles of ethylene oxide at room temperature for several hours. Twenty-five parts by volume of concentrated hydrochloric acid and 200 parts of ice are added and then 30 parts by volume of 23 percent sodium nitrite solution is allowed to flow in slowly at 0 to 5 C. The whole is stirred at the same temperature for another 2 hours and coupled with. 24.3 parts of 7-amino-l-hydroxynaphthalene-Ii-sulfonic acid as described in example l. A dark red powder of a dye having the formula S C N is obtained which dissolves in water with a red color and gives bluish red dyeings having excellent light and wet fastness properties on polyamide.

With the same coupling components and the diazo components given in the following table 2, other dyes are obtained in an equivalent way.

EXAMPLE l Thirty parts by volume of a 23 percent aqueous solution of sodium nitrite is allowed to flow slowly while stirring at 0 to 5 C. into a solution of 20.9 parts of dimethyl 3-aminophthalate in 300 parts by volume of glacial acetic acid and 24 parts by volume of concentrated hydrochloric acid. A little ice is added during the addition of the sodium nitrite solution. Tl-le whole is stirred at the same temperature for another 2 hours and any excess of nitrous acid present is removed.' A solution of the sodium salt of 24.3 parts of 7-amino-l-hydroxynaphthalene-Iisulfonic acid is added to the diazo solution and the further procedure of example 1 is followed. A dark red powder is obtained which dissolves in water to give a red coloration and produces red shades having excellent fastness properties on polyamide cloth.

Other dyes shown in the following table 3 are obtained with the same coupling component and the diazo components shown in the table by analogous procedures:

TABLE 3 Example Diazo component Shade of dyeing on polyamide red red

red bluish red red S-aminoisophthalate red I? diisobulyl aminoterephthalate bluish red l8 di-(B-ethoxyethyl) aminoteriphthulate bluish red I9 di-(flmhenoxyelhyl) aminoterephthalnte bluish red 20 dlbenzyl umlnmercphihnlale hluilh red 21 dicycluhexyl nmlnoterephlhnlntc hluinh red We claim: 1. A monoazo dye having the formula wherein R denotes alkyl of one to four carbon atoms, benzyl, phenylethyl, cyclohexyl, chloroethyl, hydroxyalkyl of up to four carbon atoms, alkoxy-alkyl of up to eight carbon atoms, methoxyethoxyethyl, ethoxyethoxyethyl or phenoxyethyl and X denotes hydrogen, sodium or potassium.

2. A monoazo dye having the formula HgN R o 0 C R OOC wherein R denotes alkyl of one to four carbon atoms, methoxyethyl, ethoxyethyl, butoxyethyl, methoxyethoxyethyl or ethoxyethoxyethyl and X denotes hydrogen, sodium or potassium.

3. The dye having the formula:

ggz gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,624,068 Dated November 30, 1971 Inventor(s) Johannes Dehnert and Gerhard Gnad It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

. "'1 Column 2, lines 4 and 5, delete "dibenzyl aminoterephthalate, dicyclohexyl aminoterephthalate".

Column 4, line 4, aminoteriphthalate" should read aminoterephthalate claim 4, that portion of the formula reading H N" should read H Signed and sealed this 9th day of May 1972.

(SEAL) Attest:

EDWARD M.FLEI'CHER, JR. ROBERT GOTTSGHALK Attesting Officer Commissioner of Patents 

2. A monoazo dye having the formula
 3. The dye having the formula:
 4. The dye having the formula: 